200407467 玖、發明說明： 發明所屬之技術領域 本發明係有關使用脈衝逆電解，從酸性溶液中沉積銅於 裝飾性基材上’以製備更爲均勻分布之鍍銅層。 先前技術 從酸性溶液中電鍍銅爲眾所周知，有許多工業上的應 用。在多數的應用上，係將被鍍物置於電極，此種技術而後 稱爲架式電鍍。 這些應用中之其中一種爲電鍍鋁合金汽車輪圈，此鋁合 金表面在浸鍍於鋅酸鹽溶液前需淸潔及去脂，留下一薄鍍鋅 層於合金表面。因爲銅電鍍溶液之酸性性質，鋅酸鹽膜在浸 鍍時會被破壞，爲避免鋅酸鹽膜之破壞，一般正常下係於鋅 酸鹽膜上施以輕度酸浴以電鍍一層薄鍍鎳層，再從高酸性溶 液中於鍍鎳層上沉積銅。鋅酸鹽/鎳之處理可促進電鍍銅至 鋁合金基材上，因爲銅無法直接電鍍。在此鋁合金汽車輪圈 之特殊實例中，常習慣鍍上一層相對厚銅膜，因在電鍍最終 鎳及鉻飾面之前，通常需將銅膜拋光。 銅沉積有兩個目的：（1 )其具有調平性質，因此可將鑄 造鋁輪圈的缺陷隱藏起來，以及（2 )其較軟且易於拋光。銅 表面之拋光可產生一平坦光面，在施行最終飾面後，看起來 較具吸引力。此外，拋光表面延展軟銅能有效地封住銅鍍層 上的孔洞，可提升鍍層之抗腐蝕性。 現今技術其中一項的缺點爲必須鍍著最小厚度之銅於 鋁基上，以確保在拋光程序時銅沉積沒有被完全移除，並且 200407467 在後續製程階段提供鋁適當的保護。然而，由於使用在酸性 銅電鍍階段之電極及添加劑的本質，鍍銅層的分布一般係不 均勻的。爲於凹陷處達到所需之最小厚度，輪圈之曝露區會 有額外的銅鑛者其上’對於電鍍者而言，這是非常浪費及耗 費成本的。 另一銅沉積之應用爲電鍍於塑膠基材上，其在汽車工業 上非常普遍。通常於這些應用，塑膠基材先經前處理以允許 其接受由無電方式電鍍之薄鎳沉積。一旦薄鎳層使得塑膠構 件成爲導電時，在施加最終鎳及鉻飾面之前使用一相當的銅 層。最小銅厚度通常由電鍍零件之最後使用者所指定，例如 汽車製造者。由於傳統裝飾性電解之銅金屬沉積分布狀態不 佳，爲於複雜元件之凹陷處達到最小銅厚度，導致曝露區之 鍍銅過量。再者，對電鍍者產生浪費銅，亦會導致如沉積突 枝或燃燒之其他問題，或由於尺寸精度的失誤而遭退件。突 枝及燃燒對於這些習於電鍍技藝係眾所周知之熟悉項目，且 這類缺點在電鍍沉積中會發生於電鍍物件之曝露區。 因此對於一可提供大幅改善鍍件表面之鍍層分布性的製 程將是有益的。藉由降低需達到最低厚度銅之製程時間以提 高產量。此外，其能減少銅耗量，且亦可減少因尺寸誤差、 銅沉積燃燒或突枝導致退件的可能性。 其他具有更均勻分布之銅沉積的應用係爲有益亦是本 發明所意圖的。 使用從酸性溶液沉積銅之脈衝逆電解技術，其係使用在 從酸性溶液中電鍍銅至印刷電路板及其他基材之電子產業 是眾所周知的。美國專利No. 6，3 1 9,3 8 4，Taylor等人，該標 200407467 的在此全部倂入本案以作爲參考資料，其揭露將銅電沉積在 半導體基材上之方法，其中該酸性銅鑛浴實質上缺乏光亮性 及/或調平性。 使用在電子應用上之添加劑的基本化學，以及其在脈衝 逆電流電鍍狀態相較於直流電狀態之性質，係由T . p e a r s 〇 n 所解釋 ’、' Effect of Pulsed Current On The Electrodeposition of Chromium and Copper"，PhD 論文，安思通大學（Aston University)，英國，1 9 8 9，該標的在此全部倂入本案以作爲 參考資料。添加劑大致類似該等使用於此一般架式電鍍之應鲁 用且槪括包含磺基丙基硫及聚乙二醇結合氯離子作用。脈衝 逆電流及這些添加劑的使用產生電化學效應，導致金屬分布 的提升。此效應促使電鍍銅進入電路板之孔洞中，這些孔洞 一般直徑約〇 · 5 mm及深度2〜3 mm，這些孔洞的有效電流 密度極低，且在如電鍍合金鋼圈之一般架式電鍍應用的正常 範圍之外。 不幸的，此分布效應可能會被其他添加劑所破壞。因爲 這原因，應用於印刷電路板之電鍍浴組成一般非常簡單且無· 法提供一全亮及調平銅沉積。相反的，在一般架式電鍍應用 上，銅沉積的表面是最重要的。因爲不使用脈衝電鍍，更調 平及光亮之添加劑效果在此分布效應上就不重要了。 應用於電子方面之電解液基本組成’與使用在傳統架式 電鍍是不同的。一般來說’使用於電子/線路板之電鍍浴含 有75g/l之硫酸銅五水合物、115nil/l之濃縮硫酸、40mg/l 之氯離子及專屬之添加劑（一種低金屬/高酸浴）°反過來 說，用於一般架式電鍍之電鍍浴含有2 2 0 g/Ι之硫酸銅五 200407467 水合物、35 ml/l之濃縮硫酸、80 mg/l之氯離子及專屬之添 加劑（一種高金屬/低酸浴）。 本發明者很驚訝的發現，脈衝逆電流電鍍技術於印刷電 路板之應用，在包括上述之鋁合金汽車輪圈及塑膠基材之一 般架式電鍍之電鍍銅時，有很好的表現。意外的是，該電.流 密度範圍非常不同於印刷電路板之應用。本發明者發現脈衝 逆電流電鍍使用於一般架式電鍍相較於傳統電鍍浴其物件 鍍著最低厚度之各種應用時，可產生較少之銅損耗。 當利用脈衝逆電鍍結合電子型式電解組成電鍍合金輪 圈時，以及一種可使脈衝逆電解最佳之添加劑系統，可導致 輪圈上的銅沉積分布大幅提升。這對電鍍者而言，有二個明 顯好處：（1)較少之多餘銅沉積產生在輪圈的曝露區，以及 (2 )輪圈之凹陷處在與前述應用相比可於較短時間下鍍上 最少厚度，因而增加生產量。 就本發明者所能知道的而言，該技術之前並沒有提出或 使用在傳統架式電鍍廠，可能是因爲使用脈衝逆電流導致被 鑛物件之鍍層於高電流密度區變得灰暗。然而，在合金汽車 輪圈的案例裡，一般銅沉積還要拋光處理，使得該負面效應 不再是個要素。或者，電鍍銅之階段可含有一段之脈衝逆電 解，繼之施以一段直流電電解，以留下較只施加脈衝逆電解 光亮之最終沉積。 此外，使用脈衝逆電解電鍍物件之低電流密度區在使用 適當之專屬添加劑時可保有一明亮之表面，因而在全物件留 下光亮表面。 200407467 因此下列所陳述之實例，脈衝逆電流技術完全適用在各 種應用，其中更爲均勻分布之銅沉積是可預期的，例如電鍍 一最小厚度之規格，如合金輪圈或電鍍汽車用塑膠零件。 發明內容 使用脈衝逆電鍍沉積銅係一種在酸性銅電鍍浴中電鍍 裝飾性物件之方法，其包含之步驟有： (a )懸置一裝飾性物件於一含有銅離子、配對離子及氯 離子之電鍍浴中；與 (b )利用脈衝逆電流電鍍該裝飾性物質一段時間，以在 該裝飾性物質至少一處之表面產生所欲厚度之 銅。 在較佳實施例中，酸性銅電鍍浴更包含聚醚及二價硫化 合物。 實施方式 本發明於利用脈衝逆電流在酸性銅電鍍浴中電鍍銅於 裝飾性物件，以在裝飾性物件表面鍍上所欲厚度之銅。本發 明特別適用於在鋁合金輪圈及汽車用塑膠零件上電鍍更爲 均勻厚度的銅。 本發明之酸性銅鍍浴一般包含銅離子、配對離子源及氯 離子。其他有助於提升銅鍍層之添加劑亦可加於浴中。 存在於電鍍浴中之銅離子，其濃度約10 g/ι至50 g/ι 。硫酸銅五水合物係爲一種銅化合物，其對本發明之 浴是有用的，雖然其他銅化合物亦見之於文獻中。電鍍浴 一般含硫酸銅五水合物之濃度約在50 g/Ι至1 00 g/l，以約 200407467 75 g/l爲佳。 電鍍浴中之配對離子源通常是硫酸鹽離子或甲磺酸。較 佳之硫酸鹽離子源爲硫酸。存在於電鍍浴中之配對離子濃度 約 5 0 - 2 5 0 m 1 /1，以約 1 0 0 - 1 5 0 m 1 /1 爲佳，最好是約 1 1 5 m 1 /1。 存在於電鍍浴之氯離子濃度約10-5 00 m g/l，以約10-500 m g/l爲佳。 在較佳實施例中，本發明之電鍍浴更包含聚醚及二價硫 化合物。 一般存在於電鍍浴之聚醚濃度約5 0-5 0 00 mg/Ι，以約300 mg/1爲佳。一般來說聚醚之分子量在500與1〇〇5〇〇〇之間。 較佳之聚醚包括聚乙二醇及一種環氧乙烷 /環氧丙烷共聚 合體。 一般存在於電鍍浴之二價硫化合物濃度約1-1 50mg/1， 以約3 0- 5 0 m g/l爲佳。較佳之二價硫化合物包括氫硫丙烷磺 酸或其鹼金屬鹽、雙（丙烷-3-磺酸）二硫化物或其鹼金屬鹽、 及雙（乙院-2-硫酸）二硫化物或其驗金屬鹽。 商業上可用之調平化合物及光亮劑亦可添加於本發明 之電鍍浴中。光亮劑及調平劑之添加係用來增進由電鍍浴中 所產生沉積的視覺性質。電鍍浴之脈衝機制由交流之陰極及 陽極脈衝所組成。陰極脈衝時間通常在5與！ 〇 〇 ms之間， 而陽極脈衝時間通常在0 . 1與1 〇 in s之間。電鍍機制可隨意 地包含最後延長之陰極時間，最長不超過1小時。 實例 下列非限制性實例可呈現本發明之各種特質。在這些實 -10- 200407467 例中，伴隨著鋼嵌板（p a n e 1)之赫耳電池試驗（H u 11 c e 11 t e s t) 係爲/利用X射線螢光技術來量測銅鍍層厚度。爲避免鋼嵌 板浸鍍上銅沉積，嵌板在轉移至赫耳電池之前需先透過氰化 物銅溶液鍍上一層最低厚度之銅（將近〇 . 1 - 〇 . 2 A m )。所有 的赫耳電池試驗利用〃 s u 1 f a s t ''施行於2 5 °C。 脈衝電流機制爲1 0 m s陰極，0. 5 m s陽極，對印刷電 路板應用來說，其爲正常脈衝機制。 實例1 - 5係說明習知技藝及顯示現行酸性銅電鍍之電 流技術。使用於這些實例之組成及電鍍條件列於下方表1。 《φ 表1.酸性銅電鍍條件習知技藝 實例1 實例2 實例3 實例4 實例5 硫酸銅五水合物 210 g/1 210 g/1 75 g/1 75 g/1 75 g/I 硫酸 32 ml/1 32 ml/1 115 ml/1 115 ml/1 115 ml/1 氯離子 85 mg/1 85 mg/1 85 mg/1 85 mg/1 75 mg/1 添加劑 Cumae 8000SL Cumae 8000SL Cumae 8000SL Cumae 8000SL 300 mg/1 PAG1 添加劑 30 mg/1 disodium salt2 電鍍型式 直流電 逆脈衝 直流電 逆脈衝 直流電 電流 1安培 ]安培 1安培 〗安培 1安培 電鍍時間 15分鐘 15分鐘 15分鐘 15分鐘 15分鐘 厚度比 6.07 ： 1 6.8 ： 1 4.0 ： 1 3.0 : 1 4.0 : 1 !PAG =聚乙二醇 2 disodium salt =雙（乙院-2 -硫酸）二硫化物二鈉鹽 實例1 製備一含有210 g/Ι硫酸銅五水合物、32 ml/1硫酸及85 m g /1氯離子之溶液。加入專屬添加劑（C u m a c 8 0 0 0 S L，·--種 用於一般架式酸性銅電鍍之M a c D e ι· m i d製程）。赫耳電池嵌 -Π - 200407467 板以直流電1安培電鍍】5分鐘。嵌板在點上測量之厚度相 當於主要電流密度2.0A/dm2及〇.lA/dm2。在2.〇A/dm2之厚 度被除以0 · 1 A / d m2之厚度得到6 · 〇 7 : 1之厚度比。經過全部 範圍之嵌板表面爲明亮的。 竇例2 製備如同實例1之溶液以及將赫耳電池嵌板利用平均電 流1安培及陽極：陰極電流密度將近3 : 1之脈衝逆電流機 制電鍍1 5分鐘。如同之前計算厚度比爲6 · 8 : 1。嵌板表面 在高電流密度區爲平滑暗淡的，低電流密度區則爲明亮的。鲁 實例3 製備一含有75g/l硫酸銅五水合物、硫酸，85 mg/1氯離子之溶液及Cumac 8000SL添加劑。赫耳電池嵌板 以直流電1安培電鍍1 5分鐘，經計算之厚度比爲4. 〇 : 1。 經過全嵌板之沉積爲完全明亮的。 實例4 製備如同實例3之溶液以及將赫耳電池嵌板利用平均電φ 流1女培及陽極·陰極電流密度將近2 ·· 1之脈衝逆電流機 制電鍍1 5分鐘。如同之前計算厚度比爲3 · 0 : 1。沉積在高 電流密度區爲平滑暗淡的，低電流密度區則爲明亮的。 實例5 製備一含有75 g/Ι硫酸銅五水合物、115 ml/1硫酸及75 mg/1氯離子之溶液。添加3 00 mg/1之聚乙二醇及3〇 mg/1 之雙（乙烷-2 -硫酸鹽）二硫化物二鈉鹽。赫耳電池嵌板以直流 電1安培電鍍1 5分鐘，經計算之厚度比爲4. 〇 : 1。經過全 -12- 200407467 範圍之沉積爲半明亮的。 實例6 - 1 2顯示本發明非限制性電鍍浴。使用於這些實例之 組成及電鍍條件列於下方表2 - 3。 表2.本發明各種銅電鍍浴 實例6 實例7 實例8 實例9 硫酸銅五水合物 75 g/1 75g/l 75 g/1 75 g/1 硫酸 115 ml/1 115 ml/1 115 ml/1 115 ml/1 氯離子 75 m g/1 75 mg/1 150 mg/1 150 mg/1 添加劑 300 mg/1 PAG MacuSpec PPR 300 mg/1 PAG 300 mg/1 PAG 添加劑 30 mg/1 disodium salt2 30 mg/1 disodium salt3 50 mg/1 disodium salt3 電鍍型式 逆脈衝 逆脈衝 逆脈衝 逆脈衝 電流 1安培 1安培 1安培 l安培 電鍍時間 15分鐘 15分鐘 15分鐘 15分鐘 厚度比 2.20 ： 1 1.9 ： 1 2.20 : 1 2.15 ： 1 PAG =聚乙二醇 disodium salt =雙（乙院-2 -硫酸）二硫化物二鈉鹽 disodium salt =雙（3 -石黃丙基）二硫化物二鈉鹽 200407467 表3.本發明各種銅電鍍浴 實例10 實例Π 實例12 硫酸銅五 水合物 75g/l 75g/l 75 g/1 硫酸 115 ml/1 115 ml/1 115 ml/1 氯離子 75 mg/1 75 mg/1 150 mg/1 添加劑 300 mg/1 PAG 丨 300 mg/1 PAG 300 mg/1 PAG 添加劑 30 mg/1 disodium salt2 30 mg/1 disodium salt3 30 mg/1 disodium salt3 添加劑 40 mg/1調平化合物A 50 mg/1調平化合物B 40 mg/1調平化合物A 電鍍型式 逆脈衝 逆脈衝 逆脈衝 電流 1安培 1安培 1安培 電鍍時間 15分鐘 15分鐘 15分鐘 厚度比 1.70 ： 1 2.20 ： 1 2.15 ： 1200407467 (ii) Description of the invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to the use of pulsed reverse electrolysis to deposit copper from an acidic solution on a decorative substrate 'to produce a more uniformly distributed copper plating layer. Prior art Copper plating from acidic solutions is well known and has many industrial applications. In most applications, the object to be plated is placed on the electrode. This technique is then called rack plating. One of these applications is electroplated aluminum alloy automotive wheel rims. The surface of this aluminum alloy needs to be cleaned and degreased before immersion in a zincate solution, leaving a thin zinc coating on the surface of the alloy. Due to the acidic nature of the copper plating solution, the zincate film will be destroyed during dip plating. In order to avoid the damage of the zincate film, it is generally normal to apply a mild acid bath on the zincate film to plate a thin layer A nickel layer, and copper is deposited on the nickel plating layer from the highly acidic solution. The zincate / nickel treatment facilitates the plating of copper onto aluminum alloy substrates because copper cannot be directly plated. In this particular example of an aluminum alloy automotive rim, it is customary to plate a relatively thick copper film, as the copper film is usually polished before the final nickel and chromium finishes are electroplated. Copper deposition has two purposes: (1) it has leveling properties, so it can hide the defects of cast aluminum wheels, and (2) it is soft and easy to polish. Polishing the copper surface produces a flat, glossy finish that looks more attractive after the final finish. In addition, the softened copper on the polished surface can effectively seal the holes in the copper plating and improve the corrosion resistance of the plating. One of the disadvantages of today's technology is that they must be plated with a minimum thickness of copper on an aluminum substrate to ensure that copper deposition is not completely removed during the polishing process, and 200407467 provides proper protection of aluminum during subsequent processing stages. However, due to the nature of the electrodes and additives used in the acid copper plating phase, the distribution of the copper plating layer is generally uneven. In order to achieve the required minimum thickness in the depression, the exposed area of the rim will have additional copper miners on it ', which is very wasteful and costly for the electroplater. Another application of copper deposition is electroplating on plastic substrates, which is very common in the automotive industry. Usually in these applications, plastic substrates are pre-treated to allow them to accept thin nickel deposits electrolessly plated. Once the thin nickel layer makes the plastic component conductive, use a comparable copper layer before applying the final nickel and chrome finish. The minimum copper thickness is usually specified by the end user of the plated part, such as a car manufacturer. Due to the poor deposition and distribution of copper metal in traditional decorative electrolysis, in order to achieve the minimum copper thickness in the depressions of complex components, excessive copper plating in the exposed area was caused. Furthermore, the waste of copper to the electroplater can also cause other problems such as deposits or burning, or be rejected due to dimensional accuracy errors. Spikes and combustion are familiar items that are well known to those skilled in electroplating, and such disadvantages occur in the exposed areas of electroplated objects during electroplating. Therefore, it would be beneficial to a process that can significantly improve the distribution of the plating on the surface of the plated part. Increase production by reducing the process time required to reach the minimum copper thickness. In addition, it can reduce copper consumption, and can also reduce the possibility of rejection due to dimensional errors, burning of copper deposits, or branching. Other applications with more uniformly distributed copper deposition are beneficial and are intended by the present invention. The pulse reverse electrolysis technology using copper deposited from an acidic solution is well-known in the electronics industry for electroplating copper from an acidic solution to printed circuit boards and other substrates. U.S. Pat. No. 6,3 1 9,3 8 4, Taylor et al., The entirety of the 200407467 is incorporated herein as a reference, which discloses a method for electrodepositing copper on a semiconductor substrate, in which the acid Copper ore baths lack substantial gloss and / or leveling properties. The basic chemistry of additives used in electronic applications, and their properties in the pulsed reverse current plating state compared to the direct current state, are explained by T. pears 〇 ',' Effect of Pulsed Current On The Electrodeposition of Chromium and Copper ", PhD dissertation, Aston University, United Kingdom, 189, the subject matter is hereby incorporated into this case for reference. Additives are roughly similar to those used in this general rack plating and include the effects of sulfopropylsulfide and polyethylene glycol combined with chloride ions. The pulsed reverse current and the use of these additives produce electrochemical effects that lead to an increase in metal distribution. This effect encourages electroplated copper to enter the holes of the circuit board. These holes are generally about 0.5 mm in diameter and 2 to 3 mm in depth. These holes have extremely low effective current density and are used in general rack plating applications such as plated alloy steel rings. Outside the normal range. Unfortunately, this distribution effect may be disrupted by other additives. For this reason, the composition of electroplating baths applied to printed circuit boards is generally very simple and cannot provide a full-bright and leveled copper deposit. In contrast, in general rack plating applications, copper-deposited surfaces are the most important. Because pulse plating is not used, the effect of more leveled and brighter additives is not important in this distribution effect. The basic composition of electrolyte used in electronics is different from that used in traditional rack plating. Generally, the electroplating bath used in electronic / circuit boards contains 75g / l copper sulfate pentahydrate, 115nil / l concentrated sulfuric acid, 40mg / l chloride ion and exclusive additives (a low metal / high acid bath) ° Conversely, the plating bath used for general rack plating contains copper sulfate 5 220407467 hydrate, 35 ml / l concentrated sulfuric acid, 80 mg / l chloride ion and exclusive additives (a kind of High metal / low acid bath). The inventor was surprised to find that the application of pulsed reverse current plating technology to printed circuit boards performed well when used in the electroplated copper plating of general aluminum alloy automobile wheels and plastic substrates. Surprisingly, this electrical current density range is very different from the application of printed circuit boards. The present inventors have found that pulsed reverse current plating can produce less copper loss when used in a variety of applications where the plating of the object has the lowest thickness compared to conventional plating baths. When pulsed reverse electroplating combined with electronic type electrolysis is used to form electroplated alloy rims, and an additive system that can optimize the pulse reverse electrolysis, the copper deposition distribution on the rim can be greatly improved. For electroplaters, there are two obvious benefits: (1) less excess copper deposits are generated in the exposed areas of the rims, and (2) the pits of the rims can be used in a shorter time compared to the previous application The minimum thickness is plated, which increases throughput. To the best of the inventor's knowledge, this technology has not been proposed or used in traditional rack plating plants before. It may be because the use of pulsed reverse current causes the coating of mineral parts to become dark in high current density areas. However, in the case of alloy car rims, copper deposits are generally polished, so that this negative effect is no longer a factor. Alternatively, the copper electroplating stage may include a period of pulsed reverse electrolysis followed by a period of DC electrolysis to leave a brighter final deposit than the pulsed reverse electrolysis. In addition, the low current density area of the articles using pulsed reverse electrolytic plating can maintain a bright surface when using appropriate proprietary additives, thus leaving a shiny surface throughout the article. 200407467 As a result of the examples given below, pulsed reverse current technology is perfectly suitable for a variety of applications, where more evenly distributed copper deposits are to be expected, such as electroplating to a minimum thickness specification, such as alloy wheels or electroplated automotive plastic parts. SUMMARY OF THE INVENTION Deposition of copper using pulsed reverse electroplating is a method for electroplating decorative objects in an acidic copper electroplating bath. The method includes the following steps: (a) Suspending a decorative object on a copper ion, pairing ion, and chloride ion In a plating bath; and (b) electroplating the decorative substance with a pulsed reverse current for a period of time to produce copper of a desired thickness on at least one surface of the decorative substance. In a preferred embodiment, the acid copper plating bath further comprises a polyether and a divalent sulfide. Embodiments In the present invention, a decorative object is electroplated with copper in an acid copper electroplating bath using a pulsed reverse current to plate a desired thickness of copper on the surface of the decorative object. The invention is particularly suitable for the plating of more uniform thickness copper on aluminum alloy wheels and plastic parts for automobiles. The acidic copper plating bath of the present invention generally contains copper ions, a paired ion source, and chloride ions. Other additives that help improve the copper plating can also be added to the bath. The concentration of copper ions present in the plating bath is about 10 g / ι to 50 g / ι. Copper sulfate pentahydrate is a copper compound that is useful for the bath of the present invention, although other copper compounds are also found in the literature. The plating bath generally contains copper sulfate pentahydrate at a concentration of about 50 g / 1 to 100 g / l, preferably about 200407467 75 g / l. The counter ion source in the plating bath is usually sulfate ion or methanesulfonic acid. A preferred source of sulfate ions is sulfuric acid. The paired ion concentration in the plating bath is about 50-2 50 m 1/1, preferably about 100-1 50 m 1/1, and most preferably about 1 15 m 1/1. The chloride ion concentration in the plating bath is about 10-5 00 m g / l, and preferably about 10-500 m g / l. In a preferred embodiment, the electroplating bath of the present invention further comprises a polyether and a divalent sulfur compound. The concentration of polyether generally present in the plating bath is about 50-500 mg / 1, and preferably about 300 mg / 1. Generally, the molecular weight of polyether is between 500 and 10,000. Preferred polyethers include polyethylene glycol and an ethylene oxide / propylene oxide copolymer. The divalent sulfur compounds generally present in the plating bath have a concentration of about 1-1 to 50 mg / 1, preferably about 30 to 50 mg / l. Preferred divalent sulfur compounds include hydrosulfopropanesulfonic acid or an alkali metal salt thereof, bis (propane-3-sulfonic acid) disulfide or an alkali metal salt thereof, and bis (Otsuno-2-sulfuric acid) disulfide or Its test metal salt. Commercially available leveling compounds and brighteners can also be added to the plating baths of the present invention. Brighteners and levelers are added to enhance the visual properties of the deposits produced in the plating bath. The pulse mechanism of the plating bath consists of alternating cathode and anode pulses. Cathode pulse time is usually between 5 and! 〇 〇 ms, and the anode pulse time is usually between 0.1 and 10 in s. The plating mechanism can optionally include the last extended cathode time, up to a maximum of 1 hour. Examples The following non-limiting examples illustrate various characteristics of the invention. In these actual -10- 200407467 cases, the Hull cell test (H u 11 c e 11 t e s t) accompanied by a steel panel (p a n e 1) is based on / using X-ray fluorescence technology to measure the thickness of copper plating. To avoid immersion plating of copper on steel panels, the panels need to be plated with a minimum thickness of copper (approximately 0.1-0.2 A m) through a copper cyanide solution before being transferred to a Herr battery. All Herr battery tests were performed using 〃 s u 1 f a s t '' at 25 ° C. The pulse current mechanism is a 10 m s cathode and 0.5 m s anode. For printed circuit board applications, it is a normal pulse mechanism. Examples 1 to 5 illustrate conventional techniques and show current technology for acid copper plating. The composition and plating conditions used in these examples are listed in Table 1 below. "Φ Table 1. Known techniques of acid copper plating conditions Example 1 Example 2 Example 3 Example 4 Example 5 Copper sulfate pentahydrate 210 g / 1 210 g / 1 75 g / 1 75 g / 1 75 g / I sulfuric acid 32 ml / 1 32 ml / 1 115 ml / 1 115 ml / 1 115 ml / 1 Chloride 85 mg / 1 85 mg / 1 85 mg / 1 85 mg / 1 75 mg / 1 Additive Cumae 8000SL Cumae 8000SL Cumae 8000SL Cumae 8000SL 300 mg / 1 PAG1 additive 30 mg / 1 disodium salt2 plating type DC reverse pulse DC reverse pulse DC current 1 amp] ampere 1 amp〗 ampere 1 amp plating time 15 minutes 15 minutes 15 minutes 15 minutes 15 minutes thickness ratio 6.07: 1 6.8: 1 4.0 ： 1 3.0: 1 4.0: 1! PAG = polyethylene glycol 2 disodium salt = bis (Yiyuan-2-sulfuric acid) disulfide disodium salt Example 1 Preparation of 210 g / 1 copper sulfate pentahydrate , 32 ml / 1 sulfuric acid and 85 mg / 1 chloride solution. Adding exclusive additives (Cumma c 8 0 0 0 S L, · --- M a c D e m · d process for general rack acid copper plating). Herr battery embedded -Π-200407467 The board is electroplated with DC 1 amp] for 5 minutes. The thickness of the panel measured at points corresponds to the main current densities of 2.0 A / dm2 and 0.1 A / dm2. The thickness ratio of 2.0A / dm2 was divided by the thickness of 0 · 1 A / dm2 to obtain a thickness ratio of 6 · 07: 1. The entire surface of the panel is bright. Sinus Example 2 A solution similar to that in Example 1 was prepared and a Herr battery panel was electroplated with an average current of 1 amp and an anode: cathode current density of nearly 3: 1 by a pulsed reverse current mechanism for 15 minutes. As previously calculated the thickness ratio is 6 · 8: 1. The panel surface is smooth and dull in high current density areas and bright in low current density areas. Example 3 A solution containing 75 g / l copper sulfate pentahydrate, sulfuric acid, 85 mg / 1 chloride ion, and Cumac 8000SL additive was prepared. 〇: 1。 Her battery panel was plated with 1 ampere of direct current for 15 minutes, and the calculated thickness ratio was 4.0: 1. The deposition through the full panel is completely bright. Example 4 A solution as in Example 3 was prepared and a Herr cell panel was electroplated for 15 minutes using a pulsed reverse current mechanism with an average electric current of 1 female and an anode-cathode current density of nearly 2 ·· 1. The thickness ratio is calculated as 3 · 0: 1 as before. Deposits are smooth and dim in high current density areas, and bright in low current density areas. Example 5 A solution containing 75 g / 1 copper sulfate pentahydrate, 115 ml / 1 sulfuric acid and 75 mg / 1 chloride ion was prepared. Add 300 mg / 1 of polyethylene glycol and 30 mg / 1 of bis (ethane-2-sulfate) disulfide disodium salt. 〇: 1。 The Herr battery panel was electroplated with 1 ampere of direct current for 15 minutes, and the calculated thickness ratio was 4.0%. After a full range of -12-200407467, the deposit is semi-bright. Examples 6-12 show non-limiting plating baths of the present invention. The composition and plating conditions used in these examples are shown in Tables 2-3 below. Table 2. Examples of various copper electroplating baths of the present invention Example 6 Example 7 Example 8 Example 9 Copper sulfate pentahydrate 75 g / 1 75g / l 75 g / 1 75 g / 1 sulfuric acid 115 ml / 1 115 ml / 1 115 ml / 1 115 ml / 1 chloride 75 mg / 1 75 mg / 1 150 mg / 1 150 mg / 1 additive 300 mg / 1 PAG MacuSpec PPR 300 mg / 1 PAG 300 mg / 1 PAG additive 30 mg / 1 disodium salt2 30 mg / 1 disodium salt3 50 mg / 1 disodium salt3 plating type reverse pulse reverse pulse reverse pulse reverse pulse current 1 amp 1 amp 1 amp 1 amp plating time 15 minutes 15 minutes 15 minutes 15 minutes thickness ratio 2.20: 1 1.9: 1 2.20: 1 2.15 : 1 PAG = polyethylene glycol disodium salt = bis (Yiyuan-2-sulfuric acid) disulfide disodium salt disodium salt = bis (3-stone yellow propyl) disulfide disodium salt 200407467 Table 3. Various coppers of the present invention Plating bath example 10 example Π example 12 copper sulfate pentahydrate 75g / l 75g / l 75 g / 1 sulfuric acid 115 ml / 1 115 ml / 1 115 ml / 1 chloride ion 75 mg / 1 75 mg / 1 150 mg / 1 Additive 300 mg / 1 PAG 丨 300 mg / 1 PAG 300 mg / 1 PAG Additive 30 mg / 1 disodium salt2 30 mg / 1 disodium salt3 30 mg / 1 disodium sa lt3 additive 40 mg / 1 leveling compound A 50 mg / 1 leveling compound B 40 mg / 1 leveling compound A plating pattern reverse pulse reverse pulse reverse pulse current 1 amp 1 amp 1 amp plating time 15 minutes 15 minutes 15 minutes thickness Ratio 1.70: 1 2.20: 1 2.15: 1
〗PAG =聚乙二醇 2 disodium salt =雙（乙院-2 -硫酸）二硫化物二鈉鹽 3 disodium salt =雙（3 -擴丙基）二硫化物二鈉鹽 實例6 製備一含有75 g/Ι硫酸銅五水合物、115 ml/1硫酸及75馨 mg/1氯離子之溶液。添加3 0 0 mg/1之聚乙二醇及30 mg/1 之雙（乙烷-2 -硫酸鹽）二硫化物二鈉鹽。赫耳電池嵌板利用平 均電流1安培及陽極：陰極電流密度將近2 : 1之脈衝逆電 流機制電鑛1 5分鐘，經計算之厚度比爲2 · 2 0 : 1。嵌板在高 電流密度區爲平滑暗淡的，低電流密度區則爲半明亮的。 實例7 製備一含有75 g/Ι硫酸銅五水合物、115 ml/1硫酸及75 -14- 200407467 mg/l氯離子之溶液。加入專屬添加劑（MacuSpec PPR，一 種用於印刷電路板電鑛之M a c D e r m i d製程）。赫耳電池嵌板 利用平均電流1女培及陽極·陰極電流密度將近2 : 1之脈 衝逆電流機制電鍍1 5分鐘，經計算之厚度比爲1 .9 : 1。沉 積在高電流密度區爲平滑暗淡的，低電流密度區則爲半明亮 的。 實例8 製備一含有75 g/Ι硫酸銅五水合物、1 1 5 ml/1硫酸及1 50 mg/1氯離子之溶液。添加3 00mg/l之聚乙二醇及30mg/l之 雙（3-磺丙基）二硫化物二鈉鹽。赫耳電池嵌板利用平均電流 1安培及陽極：陰極電流密度將近2 : 1之脈衝逆電流機制電 鍍1 5分鐘，經計算之厚度比爲2 · 2 0 : 1。沉積在高電流密度 區爲平滑暗淡的，低電流密度區則爲半明亮的。 實例9 製備一含有75 g/Ι硫酸銅五水合物、115 ml/1硫酸及75 mg/1氯離子之溶液。添加3 00 mg/1之聚乙二醇、50 mg/1之 雙（3-磺丙基）二硫化物二鈉鹽。赫耳電池嵌板利用平均電流 1安培及陽極··陰極電流密度將近2 : 1之脈衝逆電流機制電 鍍1 5分鐘，經計算之厚度比爲2.1 5 : 1。沉積在高電流密度 區爲平滑暗淡的，低電流密度區則爲半明亮的。 實例1〇 製備一含有75 g/Ι硫酸銅五水合物、1 1 5 ml/1硫酸及75 mg/1氯離子之溶液。添加3 00 mg/1之聚乙二醇、30 mg/1之 雙（乙烷-2-硫酸鹽）二硫化物二鈉鹽及40 mg/1之商業用調平 200407467 化合物A。赫耳電池嵌板利用平均電流1安培及陽極：陰 電流密度將近2 : 1之脈衝逆電流機制電鍍1 5分鐘，經計 之厚度比爲1 · 7 0 : 1。沉積在高電流密度區爲平滑暗淡的 低電流密度區則爲全明亮的。 實例1 1 製備一含有75 g/Ι硫酸銅五水合物、115 m 1/1硫酸及 mg/1氯離子之溶液。添加3 00 mg/1之聚乙二醇、30 mg/1 雙（3-磺丙基）二硫化物二鈉鹽及50 mg/1之商業用調平化 物B。赫耳電池嵌板利用平均電流1安培及陽極：陰極電 密度將近2 : 1之脈衝逆電流機制電鍍1 5分鐘，經計算之 度比爲2.2 0 : 1。嵌板表面在高電流密度區爲平滑暗淡的 低電流密度區則爲全明亮的。 實例12 製備一含有75 g/Ι硫酸銅五水合物、1 1 5 ml/1硫酸及 mg/1氯離子之溶液。添加3 00 mg/1之聚乙二醇、30 mg/1 雙（3-磺丙基）二硫化物二鈉鹽及40 mg/1之商業用調平化 物A。赫耳電池嵌板利用平均電流1安培及陽極：陰極電 密度將近2 ·· 1之脈衝逆電流機制電鍍1 5分鐘’隨後施t 安培直流電5分鐘。經計算之厚度比爲2 · 1 5 : 1。經過全 板之沉積爲明亮的。 圖式簡單說明：無 極 算 75 之 合 流 厚 75 之 合 流 I 1 嵌 -16 -〖PAG = polyethylene glycol 2 disodium salt = bis (Yiyuan-2-sulfuric acid) disulfide disodium salt 3 disodium salt = bis (3-propane) disulfide disodium salt Example 6 Preparation 1 contains 75 A solution of g / 1 copper sulfate pentahydrate, 115 ml / 1 sulfuric acid and 75 mg mg / 1 chloride. Add 300 mg / 1 polyethylene glycol and 30 mg / 1 bis (ethane-2 -sulfate) disulfide disodium salt. The Herr battery panel utilizes a pulsed reverse current mechanism with an average current of 1 amp and an anode: cathode current density of nearly 2: 1 for 15 minutes. The calculated thickness ratio is 2 · 2 0: 1. Panels are smooth and dim in high current density areas and semi-bright in low current density areas. Example 7 A solution containing 75 g / 1 copper sulfate pentahydrate, 115 ml / 1 sulfuric acid, and 75-14-200407467 mg / l chloride ion was prepared. Add exclusive additives (MacuSpec PPR, a Ma c D e r m i d process for printed circuit board power mining). The Herr battery panel uses an average current of 1 female and an anode / cathode current density of nearly 2: 1. The pulse reverse current mechanism is used for electroplating for 15 minutes, and the calculated thickness ratio is 1.9: 1. The deposition is smooth and dim in the high current density area and semi-bright in the low current density area. Example 8 A solution containing 75 g / 1 copper sulfate pentahydrate, 115 ml / 1 sulfuric acid, and 150 mg / 1 chloride ion was prepared. Add 300 mg / l of polyethylene glycol and 30 mg / l of bis (3-sulfopropyl) disulfide disodium salt. The Herr battery panel was electroplated for 15 minutes using a pulsed reverse current mechanism with an average current of 1 amp and an anode: cathode current density of nearly 2: 1, and the calculated thickness ratio was 2.20: 1. Deposition in the high current density area is smooth and dim, and the low current density area is semi-bright. Example 9 A solution containing 75 g / 1 copper sulfate pentahydrate, 115 ml / 1 sulfuric acid and 75 mg / 1 chloride ion was prepared. Add 300 mg / 1 polyethylene glycol and 50 mg / 1 bis (3-sulfopropyl) disulfide disodium salt. The Herr battery panel was electroplated for 15 minutes using a pulsed reverse current mechanism with an average current of 1 amp and an anode · cathode current density of nearly 2: 1, and the calculated thickness ratio was 2.15: 1. Deposition in the high current density area is smooth and dim, and the low current density area is semi-bright. Example 10 A solution containing 75 g / 1 copper sulfate pentahydrate, 115 ml / 1 sulfuric acid, and 75 mg / 1 chloride ion was prepared. Add 300 mg / 1 of polyethylene glycol, 30 mg / 1 of bis (ethane-2-sulfate) disulphide disodium salt and 40 mg / 1 of commercial level 200407467 Compound A. The Herr battery panel uses a pulsed reverse current mechanism with an average current of 1 amp and an anode: negative current density of nearly 2: 1 for 15 minutes, and the thickness ratio is calculated as 1.70: 1. The deposition in the high current density area is smooth and dim, and the low current density area is completely bright. Example 1 1 A solution containing 75 g / 1 copper sulfate pentahydrate, 115 m 1/1 sulfuric acid and mg / 1 chloride ion was prepared. Add 300 mg / 1 polyethylene glycol, 30 mg / 1 bis (3-sulfopropyl) disulfide disodium salt, and 50 mg / 1 commercial leveling compound B. The Herr battery panel was electroplated for 15 minutes using a pulsed reverse current mechanism with an average current of 1 amp and an anode: cathode density of nearly 2: 1, and the calculated ratio was 2.20: 1. The surface of the panel is smooth and dim in the high current density area, and it is fully bright in the low current density area. Example 12 A solution containing 75 g / 1 copper sulfate pentahydrate, 115 ml / 1 sulfuric acid, and mg / 1 chloride ion was prepared. Add 300 mg / 1 polyethylene glycol, 30 mg / 1 bis (3-sulfopropyl) disulfide disodium salt and 40 mg / 1 commercial leveling compound A. The Herr battery panel uses a pulsed reverse current mechanism with an average current of 1 Ampere and an anode: cathode density of nearly 2 ·· 1 for 15 minutes' followed by applying t Ampere DC for 5 minutes. The calculated thickness ratio is 2 · 1 5: 1. The deposition through the board is bright. Simple illustration of the diagram: Promise 75 confluence thick 75 confluence I 1 embedded -16-